Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
  • H05K3/207—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern using a prefabricated paste pattern, ink pattern or powder pattern
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
  • H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
  • H05K3/046—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/24—Reinforcing the conductive pattern
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/24—Reinforcing the conductive pattern
  • H05K3/245—Reinforcing conductive patterns made by printing techniques or by other techniques for applying conductive pastes, inks or powders; Reinforcing other conductive patterns by such techniques
  • H05K3/246—Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
  • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
  • H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/03—Conductive materials
  • H05K2201/0332—Structure of the conductor
  • H05K2201/0335—Layered conductors or foils
  • H05K2201/0347—Overplating, e.g. for reinforcing conductors or bumps; Plating over filled vias
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/05—Patterning and lithography; Masks; Details of resist
  • H05K2203/0502—Patterning and lithography
  • H05K2203/0528—Patterning during transfer, i.e. without preformed pattern, e.g. by using a die, a programmed tool or a laser
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
  • H05K2203/107—Using laser light

Definitions

• the invention relates to a method for producing electrically conductive surfaces on a non-conductive substrate.
• the method according to the invention is suitable, for example, for conductor tracks on printed circuit boards, RFI D antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, foil conductors, conductor tracks in solar cells or in LCD or plasma picture screens, 3D Molded Interconnect Devices, integrated circuits, resistive, capacitive or inductive elements, diodes, transistors, sensors, actuators, optical components, receiver / transmitter devices, decorative or functional surfaces on products used to shield electromagnetic radiation, for heat conduction or as packaging, thin metal foils or a - or produce two-sided laminated polymer support. Also can be produced in any form with the method galvanically coated products.
• a method for producing electrically conductive surfaces on a substrate is known, for example, from US-B 6,177,151.
• electrically conductive particles which are contained in a matrix material are transferred from a carrier to the substrate.
• the transmission takes place by irradiation with a laser.
• the laser volatilizes the matrix material so that the transfer material is transferred to the substrate.
• the transfer material and the matrix material initially form a solid coating on the support. If the melting point of the matrix material is below the ambient temperature, it is described to freeze the carrier with the matrix material in order to solidify the matrix material.
• WO 99/44402 likewise discloses a method for producing electrically conductive surfaces on a substrate.
• a carrier on which the coating material is applied, is brought into contact with a substrate or in the vicinity of the substrate.
• a laser beam melts the coating material and transfers the molten material to the substrate.
• a high energy input is necessary so that the entire coating material is melted.
• the object of the invention is to provide an alternative method by which electrically conductive, structured or full-surface surfaces can be produced on a carrier, wherein these surfaces are homogeneous and continuously electrically conductive.
• the object is achieved by a method for producing electrically conductive surfaces on an electrically nonconductive substrate, which comprises the following steps:
• a substrate to which the electrically conductive surface is applied for example, rigid or flexible substrates are suitable.
• the substrate is not electrically conductive. This means that the specific resistance is more than 10 9 ohm x cm.
• Suitable substrates are, for example, reinforced or unreinforced polymers, as are commonly used for printed circuit boards.
• Suitable polymers are epoxy resins, or modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, aramid-reinforced or glass-fiber reinforced or paper-reinforced epoxy resins (for example FR4), glass fiber reinforced plastics, liquid cristal polymers (LCP), polyphenylene sulfides (PPS), polyoxymethylenes (POM), polyaryletherketones (PAEK), polyetheretherketones (PEEK), polyamides (PA), polycarbonates (PC), polybutylene terephthalates (PBT), polyethylene terephthalates (PET), polyimides (PI) , Polyimide resins, cyanoester, bismaleimide-triazine resins, nylon, vinyl ester resins, polyesters, polyester resins, polyanilines, phenolic resins, polypyrroles, polyethylene naphthalate (PEN), polymethyl methacrylate, polyethylene di
• suitable substrates composites foam-like polymers, Styropor® ®, styrodur ®, polyurethanes (PU), ceramic surfaces, textiles, paperboard, cardboard, paper, polymer coated paper, wood, mineral materials, silicon, glass, plant tissue and animal tissue.
• suitable substrates composites foam-like polymers, Styropor® ®, styrodur ®, polyurethanes (PU), ceramic surfaces, textiles, paperboard, cardboard, paper, polymer coated paper, wood, mineral materials, silicon, glass, plant tissue and animal tissue.
• a dispersion containing electroless and / or electrodepositable particles is transferred from a carrier to the substrate.
• the transfer takes place by irradiation of the dispersion on the support with a laser.
• the dispersion Before the dispersion is transferred with the electrolessly and / or electrolytically coatable particles contained therein, this is preferably applied over the entire surface of the carrier. Alternatively, it is of course also possible that the dispersion structured on the carrier is applied. However, a full-surface application of the dispersion is preferred.
• Suitable carriers are all transparent to the respective laser radiation materials, such as plastic or glass.
• plastic or glass For example, when using IR lasers, polyolefin films, PET films, polyimide films, polyamide films, PEN films, polystyrene films, or glass can be used.
• the carrier can be both rigid and flexible. Furthermore, the carrier can be in the form of a tube or endless foil, sleeve or flat carrier.
• Suitable laser beam sources for generating the laser beam are commercially available. In principle, all laser beam sources can be used. Such laser beam sources are, for example, pulsed or continuous gas, solid-state, diode or excimer lasers. These can be used in each case if the respective carrier is transparent to the laser radiation, and the dispersion containing the electrolessly and / or electrolytically coatable particles and applied to the carrier, the laser radiation is sufficiently absorbed by conversion of light into heat energy create a cavitation bubble in the base layer.
• IR lasers for example Nd-YAG lasers, Yb: YAG lasers, fiber or diode lasers. These are inexpensive and available with high performance. Particularly preferred are continuous (cw) IR lasers. Depending on the absorption behavior of the dispersion, which contains the electrolessly and / or electrolytically coatable particles, however, it is also possible to use lasers with wavelengths in the visible or in the UV frequency range. For example, Ar lasers, HeNe lasers, frequency-multiplied IR solid-state lasers or excimer lasers such as ArF lasers, KrF lasers, XeCI lasers or XeF lasers are suitable for this purpose.
• Ar lasers, HeNe lasers, frequency-multiplied IR solid-state lasers or excimer lasers such as ArF lasers, KrF lasers, XeCI lasers or XeF lasers are suitable for this purpose.
• the focal diameter of the laser beam is in the range between 1 ⁇ m and 100 ⁇ m.
• the desired parts of the dispersion applied to the support and containing the electrolessly and / or electrolytically coatable particles are transferred onto the substrate by means of a laser focused on the dispersion.
• the laser beam and / or the carrier and / or the substrate can be moved.
• the laser beam can for Example be moved by a known to the expert optics with rotating mirrors.
• the support may, for example, be in the form of a rotating endless film, which is continuously coated with the dispersions containing the electrolessly and / or electrolytically coatable particles.
• the substrate can be moved, for example, by means of an XY table or as an endless film with unwinding and winding device.
• An advantage of the method according to the invention is that, for example, in addition to two-dimensional and three-dimensional electronic circuit carriers, for example, 3D-Molded interconnect devices can be produced. It is also possible to provide the interior of device housings with tracks with extremely fine structure. For example, in the manufacture of three-dimensional objects, each surface can be processed sequentially by either placing the article in the correct position or by controlling the laser beam accordingly.
• the dispersion transferred from the support to the substrate generally contains electroless and / or electrodepositable particles in a matrix material.
• the electrolessly and / or electrolytically coatable particles may be particles of any desired geometry of any electrically conductive material, of mixtures of different electrically conductive materials or of mixtures of electrically conductive and non-conductive materials.
• Suitable electrically conductive materials are, for example, carbon, such as carbon black, graphite, graphene or carbon nanotubes, electrically conductive metal complexes, conductive organic compounds or conductive polymers or metals.
• suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCo, NiPb, ZnFe, ZnNi, ZnCo and ZnMn.
• the electrolessly and / or electrolytically coatable particles preferably have an average particle diameter of from 0.001 to 100 ⁇ m, preferably from 0.005 to 50 ⁇ m and particularly preferably from 0.01 to 10 ⁇ m.
• the average particle diameter can be determined by means of laser diffraction measurement, for example on a Microtrac X100 device.
• the distribution of the particle diameter depends on their production method. Typically, the diameter distribution has only one maximum, but several maxima are also possible.
• the surface of the electrolessly and / or electrolytically coatable particles can at least partially be provided with a coating ("coating") may be inorganic or organic in nature.
• Inorganic coatings are, for example, SiO 2 , phosphates or phosphides.
• the electrolessly and / or electrolytically coatable particles may also be coated with a metal or metal oxide.
• the metal may be in partially oxidized form.
• the metals are selected from the group consisting of aluminum, iron, copper, nickel and zinc.
• the electrolessly and / or electrolytically coatable particles may also contain a first metal and a second metal, wherein the second metal is in the form of an alloy with the first metal or one or more other metals, or contain the electrolessly and / or electrolytically coatable particles two different alloys.
• the shape of the particles has an influence on the properties of the dispersion after coating.
• the shape of the electrolessly and / or electrolytically coatable particles may be, for example, acicular, cylindrical, platelet-shaped or spherical. These particle shapes represent idealized shapes, wherein the actual shape, for example due to production, may vary more or less strongly therefrom.
• drop-shaped particles in the context of the present invention are a real deviation of the idealized spherical shape.
• Electroless and / or electroplated particles having various particle shapes are commercially available.
• the individual mixing partners can also have different particle shapes and / or particle sizes. It is also possible to use mixtures of only one type of electrolessly and / or electrolytically coatable particles having different particle sizes and / or particle shapes. In the case of different particle shapes and / or particle sizes, the metals aluminum, iron, copper, nickel and zinc as well as carbon are likewise preferred.
• mixtures of spherical particles with platelet particles are preferred.
• spherical carbonyl iron powder particles with flake-promoting iron and / or copper particles and / or carbon particles of other geometries are preferred.
• the electrolessly and / or electrolytically coatable particles in the form of their powders can be added to the dispersion.
• Such powders for example metal powders
• Such powders are common commercial products and can be easily prepared by known methods, for example by electrolytic deposition or chemical reduction from solutions of metal salts or by reduction of an oxidic powder, for example by means of hydrogen, by spraying or atomizing a molten metal, in particular Cooling media, such as gases or water. Preference is given to the gas and water atomization and the reduction of metal oxides.
• Metal powders of the preferred grain size can also be made by grinding coarser metal powders. For this purpose, for example, a ball mill is suitable.
• the carbonyl iron powder process for producing carbonyl iron powder is preferred. This is done by thermal decomposition of iron pentacarbonyl. This is described, for example, in LJ Iimann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A14, page 599.
• the decomposition of the iron pentacarbonyl can be carried out, for example, at elevated temperatures and elevated pressures in a heatable decomposer comprising a tube made of a refractory material such as quartz glass or V2A steel in a preferably vertical position, that of a heater, for example consisting of heating baths, heating wires or a Surrounded by a heating medium heating jacket is surrounded.
• Carbonyl nickel powder can also be prepared by a similar method.
• Platelet-shaped electrolessly and / or electrolytically coatable particles can be controlled by optimized conditions in the production process or subsequently obtained by mechanical treatment, for example by treatment in a stirred ball mill.
• the proportion of electrolessly and / or electrolytically coatable particles is in the range from 20 to 98% by weight.
• a preferred range of the proportion of electrolessly and / or electrolytically coatable particles is from 30 to 95% by weight, based on the total weight of the dried coating.
• Suitable matrix materials are, for example, binders with pigment-affine anchoring groups, natural and synthetic polymers and their derivatives, natural resins and synthetic resins and their derivatives, natural rubber, synthetic rubber, proteins. ne, cellulose derivatives, drying and non-drying oils and the like. These can - but need not - be chemically or physically curing, for example air-hardening, radiation-curing or temperature-curing.
• the matrix material is a polymer or polymer mixture.
• Preferred polymers as the matrix material are ABS (acrylonitrile-butadiene-styrene); ASA (acrylonitrile-styrene-acrylate); acrylated acrylates; alkyd resins; Alkylvinylacetate; Alkylenvi- nylacetat copolymers, in particular methylene vinyl acetate, ethylene vinyl acetate, butylene vinyl acetate; Alkylenvinylchlorid copolymers; amino resins; Aldehyde and ketone resins; Cellulose and cellulose derivatives, in particular hydroxyalkylcellulose, cellulose esters, such as acetates, propionates, butyrates, carboxyalkylcelluloses, cellulose nitrate; Epoxy acrylates; epoxy resins; modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic
• Particularly preferred polymers as matrix material are acrylates, acrylate resins, cellulose derivatives, methacrylates, methacrylate resins, melamine and amino resins, polyalkylenes, Polyimides, epoxy resins, modified epoxy resins, for example bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, vinyl ethers, and phenolic resins, polyurethanes, polyesters, polyvinyl acetals, polyvinyl acetates, polystyrenes, polystyrene copolymers, polystyrene acrylates, styrene-butadiene block copolymers, alkylene vinyl acetates and vinyl chloride copolymers, polyamides and their copolymers.
• the matrix material for the dispersion is preferably thermally or radiation-curing resins, for example modified epoxy resins, such as bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, cyanate esters, vinyl ethers, phenolic resins, polyimides, melamine resins and amino resins, polyurethanes, polyesters and cellulose derivatives.
• modified epoxy resins such as bifunctional or polyfunctional bisphenol A or bisphenol F resins, epoxy novolac resins, brominated epoxy resins, cycloaliphatic epoxy resins; aliphatic epoxy resins, glycidyl ethers, cyanate esters, vinyl ethers, phenolic resins, polyimides, melamine resins and amino resins, polyurethanes, polyesters and cellulose derivatives.
• the proportion of the organic binder component is from 0.01 to 60% by weight.
• the proportion is 0.1 to 45 wt .-%, more preferably 0.5 to 35 wt .-%.
• the dispersion may furthermore be admixed with a solvent or a solvent mixture in order to adjust the viscosity of the dispersion which is suitable for the respective application method.
• Suitable solvents are, for example, aliphatic and aromatic hydrocarbons (for example n-octane, cyclohexane, toluene, xylene), alcohols (for example methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, amyl alcohol), polyhydric alcohols, such as glycerol, ethylene glycol, propylene glycol, neopentyl glycol, alkyl esters (for example methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, 3-methylbutanol), alkoxy alcohols (for example methoxypropanol, methoxybutanol, ethoxypropanol), alkylbenzenes (cf.
• aliphatic and aromatic hydrocarbons for example n-octane,
• Preferred solvents are alcohols (for example ethanol, 1-propanol, 2-propanol, butanol), alkoxyalcohols (for example methoxypropanol, ethoxypropanol, butylglycol, butyldiglycol), butyrolactone, diglycol dialkyl ethers, diglycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ethers, esters (for example ethyl acetate , Butyl acetate, butyl glycol acetate, butyl diglycol acetate, diglycol alkyl ether acetates, dipropylene glycol alkyl ether acetates, DBE, propylene glycol methyl ether acetate), ethers (for example tetrahydrofuran), polyhydric alcohols such as glycerol, ethylene glycol, propylene glycol, neopen
• liquid matrix materials for example liquid epoxy resins, acrylate esters
• the respective viscosity can alternatively also be adjusted via the temperature during application, or via a combination of solvent and temperature.
• the dispersion may further contain a dispersant component. This consists of one or more dispersants.
• dispersants known to the person skilled in the art for use in dispersions and described in the prior art are suitable.
• Preferred dispersants are surfactants or surfactant mixtures, for example anionic, cationic, amphoteric or nonionic surfactants.
• Cationic and anionic surfactants are described, for example, in “Encyclopedia of Polymer Science and Technology”, J. Wiley & Sons (1966), Vol. 5, pp. 816-818, and in “Emulsion Polymerization and Emulsification Polymers", editors P. Lovell and M. El-Asser, published by Wiley & Sons (1997), pages 224 to 226.
• the dispersant may be used in the range of 0.01 to 50% by weight based on the total weight of the dispersion.
• the proportion is 0.1 to 25 wt .-%, particularly preferably 0.2 to 10 wt .-%.
• the dispersion of the invention may contain a filler component.
• the filler component of the metallizable mass may contain fibrous, layered or particulate fillers. containing their mixtures. These are preferably commercially available products, such as mineral fillers.
• fillers or reinforcing materials such as glass powder, mineral fibers, whiskers, aluminum hydroxide, metal oxides such as alumina or iron oxide, mica, quartz powder, calcium carbonate, barium sulfate, titanium dioxide or wollastonite can be used.
• thixotropic agents for example silicic acid, silicates, such as aerosils or bentonites or thixotropic agents and thickeners, for example polyacrylic acid, polyurethanes, hydrogenated castor oil, dyes, fatty acids, fatty acid amides, plasticizers, wetting agents, defoamers, lubricants , Driers, crosslinkers, photoinitiators, complexing agents, waxes, pigments, conductive polymer particles, can be used.
• thixotropic agents for example silicic acid, silicates, such as aerosils or bentonites or thixotropic agents and thickeners, for example polyacrylic acid, polyurethanes, hydrogenated castor oil, dyes, fatty acids, fatty acid amides, plasticizers, wetting agents, defoamers, lubricants , Driers, crosslinkers, photoinitiators, complexing agents, waxes, pigments, conductive polymer particles, can be used.
• the proportion of the filler and additive component based on the total weight of the dry coating is preferably 0.01 to 50 wt .-%. Further preferred are 0.1 to 30 wt .-%, particularly preferably 0.3 to 20 wt .-%.
• processing aids and stabilizers such as UV stabilizers, lubricants, corrosion inhibitors and flame retardants can be present in the dispersion according to the invention.
• their proportion based on the total weight of the dispersion 0.01 to 5 wt .-%.
• the proportion is 0.05 to 3 wt .-%.
• the electrolessly and / or electrolytically coatable particles in the dispersion on the support itself do not sufficiently absorb the energy of the energy source, for example the laser, absorbers can be added to the dispersion.
• the absorbent is either added to the dispersion or it is attached between the carrier and the dispersion, an additional separate absorption layer containing the absorbent. In the latter case, the energy is absorbed locally in the absorption layer and transferred to the dispersion by conduction.
• Suitable absorbents for laser radiation have a high absorption in the range of the laser wavelength.
• absorbers are suitable which have a high absorption in the near infrared as well as in the longer wave VIS range of the electromagnetic spectrum.
• Such absorbents are particularly suitable for absorbing the radiation of high-performance solid-state lasers, for example play Nd-Y AG lasers and IR diode lasers.
• suitable absorbents for the laser radiation are highly absorbing dyes in the infrared spectral range, for example phthalocyanines, naphthalocyanines, cyanines, quinones, metal complex dyes, such as dithiolenes or photochromic dyes.
• suitable absorbents are inorganic pigments, in particular intensively colored inorganic pigments such as chromium oxides, iron oxides, iron oxide hydrates or carbon in the form of, for example, carbon black, graphite, graphene or carbon nanotubes.
• Particularly suitable as absorbers for laser radiation are finely divided carbon species and finely divided lanthanum hexaboride (LaB 6 ).
• 0.005 to 20% by weight of absorbent based on the weight of the electrolessly and / or electrolytically coatable particles, is used in the dispersion.
• the amount of absorbent added is chosen by the person skilled in the art, depending on the respectively desired properties of the dispersion layer.
• the skilled person will further take into account that the added absorbents not only affect the speed and efficiency of the dispersion of the dispersion by the laser, but also other properties such as the adhesion of the dispersion on the support, the curing or the electroless and / or galvanic coatability of the base layer.
• the absorption layer In the case of a separate absorption layer this consists in the best case of the absorbent and a thermally stable, optionally crosslinked, material, so that it is not decomposed itself under the action of the laser light.
• the absorption layer In order to effect an effective conversion of light energy into heat energy and to achieve poor heat conduction into the base layer, the absorption layer should be applied as thinly as possible and the absorption medium should be present in the highest possible concentration, without negatively affecting the layer properties, for example adhesion to the support to influence. Suitable concentrations of the absorbent in the absorption layer are at least 25 to 95 wt .-%, preferably 50 to 85 wt .-%.
• the energy needed to transfer the portion of the dispersions containing the electroless and / or electrodepositable particles may be either on the dispersion coated side, depending on the laser used and / or the material from which the support is made on the dispersion be applied opposite side. If necessary, a combination of both process variants can be used.
• the transfer of the components of the dispersion from the support to the substrate can be carried out both on one side and on both sides.
• the two sides can be coated simultaneously with the dispersion in succession or, for example, by using two laser sources and two carriers coated with the dispersion, also from both sides.
• the dispersion is applied to the support before transferring the dispersion from the support to the substrate.
• the application is carried out, for example, by a coating method known to the person skilled in the art.
• coating methods include, for example, casting such as curtain coating, roll coating, brushing, knife coating, brushing, spraying, dipping or the like.
• the dispersion containing the electrolessly and / or electrolytically coatable particles is printed on the carrier by any printing process.
• the printing process by which the dispersion is printed is, for example, a roll or sheet-fed printing process, for example screen printing, gravure printing, flexographic printing, letterpress printing, pad printing, inkjet printing, offset printing or magnetographic printing processes.
• the dispersion is not completely dried on the support and / or cured, but transferred to the substrate in a wet state.
• the dispersion is stirred and / or recirculated in a receiver tank prior to application to the support.
• it is preferred for adjusting the viscosity of the dispersion if the feed tank, in which the dispersion is contained, can be tempered.
• the carrier is designed as an endless belt transparent to the respective laser radiation, which is moved, for example, by means of internal transport rollers.
• the carrier it is also possible to carry out the carrier as a cylinder, wherein the cylinder can be moved via inner transport rollers or is driven directly.
• the coating of the carrier with the The dispersion containing electrolessly and / or electrolytically coatable particles is then carried out, for example, by a method known to the person skilled in the art, for example with a roller or a roller system from a storage container in which the dispersion is located. By rotation of the roller or the roller system, the dispersion is absorbed and applied to the carrier. By moving the carrier past the coating roller, a full-surface dispersion layer is applied to the carrier.
• the laser beam source is arranged inside the endless belt or the cylinder.
• the laser beam is focused onto the dispersion layer and strikes the dispersion through the transparent carrier and, at the point where it encounters the dispersion, transfers the dispersion to the substrate.
• Such a commissioned work is described for example in DE-A 37 02 643.
• the transfer of the dispersion takes place, for example, in that the dispersion is at least partially evaporated by the energy of the laser beam and the dispersion is transferred by the resulting gas bubble.
• the dispersion not transferred from the support to the substrate can be reused in a next coating step.
• the layer thickness of the base layer which is transferred to the substrate by means of the transfer by the laser, preferably varies in the range between 0.01 and 50 ⁇ m, more preferably between 0.05 and 30 ⁇ m and particularly preferably between 0.1 and 20 ⁇ m.
• the base layer can be applied both over the entire surface as well as structured.
• a structured application of the dispersion to the carrier is advantageous if certain structures are to be produced in large quantities and the structured application reduces the amount of dispersion which has to be applied to the carrier. This makes it possible to achieve a more cost-effective production.
• the dispersion with which the structured or full-surface base layer is applied to the substrate cures at least partially after application.
• the curing takes place, for example, by the action of heat, light (UVA / is) and / or radiation, for example infrared radiation, electron radiation, gamma radiation, X-radiation, microwaves.
• a suitable activator must be added to trigger the curing reaction.
• Curing can also be achieved by combining various methods, for example by combining UV radiation and heat. The combination of the curing processes can be carried out simultaneously or sequentially.
• the layer first only be hardened, so that the structures formed no longer flow apart. Thereafter, the layer can be cured by exposure to heat. The heat can be done directly after the UV-curing and / or after the galvanic metallization. After the at least partial drying and / or curing of the structure transferred by laser energy to the target substrate, in a preferred variant, the electrically conductive particles can be at least partially exposed. In order to produce the continuously electrically conductive surface on the substrate, after exposing the electrically conductive particles, at least one metal layer is formed on the structured or full-surface base layer by electroless and / or galvanic coating. The coating can be carried out by any method known to those skilled in the art.
• any conventional metal coating can be applied by the method of coating.
• the composition of the electrolyte solution used for the coating depends on which metal the base layer is to be coated on the substrate.
• all metals that are nobler or the same as the least noble metal of the dispersion can be used for electroless and / or galvanic coating.
• Typical metals which are deposited by electroless and / or electroplating on electrically conductive surfaces are, for example, gold, nickel, palladium, platinum, silver, tin, copper or chromium.
• the thicknesses of the one or more deposited layers are in the usual ranges known to those skilled in the art.
• Suitable electrolyte solutions which can be used for coating electrically conductive structures are known to the person skilled in the art, for example, from Werner Jillek, Gustl Keller, Handbuch der Porterplattentechnik, Eugen G. Leuze Verlag, 2003, Vol. 4, pages 332 to 252.
• the electrolessly and / or electrically coatable particles are for the most part within the matrix, so that no continuous electrically conductive surface has yet been produced it is necessary to coat the structured or full-surface base layer applied to the substrate with an electrically conductive material. This is generally done by an electroless and / or electroplated coating.
• the matrix material can be cured by chemical means, for example by polymerization, polyaddition or polycondensation of the matrix material are, for example, by UV radiation, electron radiation, microwave radiation, IR radiation or temperature, or dried by purely physical means by evaporation of the solvent. A combination of drying by physical and chemical means is possible.
• the electrolessly and / or electrolytically coatable particles contained in the dispersion can be at least partially exposed in order to obtain already electroless and / or electrolytically coatable nucleation sites at which the following electroless and / or galvanic coating can deposit the metal ions to form a metal layer.
• the particles consist of materials which oxidize easily, it may additionally be necessary to at least partially remove the oxide layer beforehand.
• the removal of the oxide layer can already take place simultaneously with the onset of metallization, without the need for an additional process step.
• the exposure of the electrolessly and / or electrolytically coatable particles can be effected both mechanically, for example by brushing, grinding, milling, sandblasting or supercritical carbon dioxide irradiation, physically, for example by heating, laser, UV light, corona discharge or plasma discharge, or chemically.
• a chemical exposure it is preferable to use a suitable chemical or chemical mixture for the matrix material.
• the matrix material for example by a solvent on the surface at least partially dissolved and washed down or can be destroyed by means of suitable reagents, the chemical structure of the matrix material, at least in part, whereby the electroless and / or galvanically coatable particles are exposed.
• Reagents that swell the matrix material are also suitable for exposing the electrolessly and / or electrolytically coatable particles.
• swelling arise cavities in which the deposited metal ions can penetrate from the electrolyte solution, whereby a larger number of electroless and / or electrodepositable particles can be metallized.
• the adhesion, the homogeneity and the continuity of the subsequently electrolessly and / or electrodeposited metal layer is significantly better than in the case of the processes described in the prior art. Due to the higher number of exposed electrically conductive particles, the process speed in the metallization is also significantly higher, whereby additional cost advantages can be achieved.
• the matrix material is, for example, an epoxy resin, a modified epoxy resin, an epoxy novolac, a polyacrylic acid ester, ABS, a styrene-butadiene copolymer or a polyether
• the release of the currentless and / or electroplated coating takes place.
• ren particles preferably with an oxidizing agent. The oxidizing agent breaks up bonds in the matrix material, which allows the binder to be peeled off and thereby expose the particles.
• Suitable oxidizing agents are, for example, manganates such as potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen, oxygen in the presence of catalysts such as manganese, molybdenum, bismuth, tungsten and cobalt salts, ozone, vanadium pentoxide, selenium dioxide, Ammonium polysulfide solution, sulfur in the presence of ammonia or amines, manganese dioxide, potassium ferrate, dichromate / sulfuric acid, chromic acid in sulfuric acid or in acetic acid or in acetic anhydride, nitric acid, hydroiodic acid, hydrobromic acid, pyridinium dichromate, chromic acid-pyridine complex, chromic anhydride, chromium ( VI) oxide, periodic acid, lead tetraacetate, quinone, methylquinone, anthraquinone, bromine, chlorine, fluorine, iron (III) salt solutions
• manganates such as potassium permanganate, potassium manganate, sodium permanganate; Sodium manganate, hydrogen peroxide, N-methyl-morpholine N-oxide, percarbonates, for example sodium or potassium percarbonate, perborates, for example sodium or potassium perborate; Persulfates, for example sodium or potassium persulfate; Sodium, potassium and ammonium peroxodis and monosulfates, sodium hypochlorite, urea-hydrogen peroxide adducts, salts of oxohalogenic acids, such as, for example, chlorates or bromates or iodates, salts of halogenated acids, for example sodium periodate or sodium perchlorate, tetrabutylammonium peroxydisulfate, quinones , Iron (III) salt solutions, vanadium pentoxide, pyridinium dichromate, hydrochloric acid, bromine, chlorine, dichromate.
• Iron (III) salt solutions vanadium pen
• potassium permanganate potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide and its adducts
• perborates percarbonates, persulfates, peroxodisulfates, sodium hypochlorite and perchlorates.
• acidic or alkaline chemicals and / or chemical mixtures are, for example, concentrated or dilute acids, such as hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid. Also organic acids, such as formic acid or acetic acid, may be suitable depending on the matrix material.
• Suitable alkaline chemicals and / or chemical mixtures are, for example, bases, such as sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or carbonates, for example sodium carbonate or potassium carbonate.
• bases such as sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide or carbonates, for example sodium carbonate or potassium carbonate.
• the temperature may be increased during the process.
• Solvents can also be used to expose the electrolessly and / or electrolytically coatable particles in the matrix material.
• the solvent must be matched to the matrix material as the matrix material must dissolve in the solvent or swell through the solvent. If a solvent is used in which the matrix material dissolves, the base layer is only brought into contact with the solvent for a short time, so that the upper layer of the matrix material is dissolved and thereby becomes detached.
• Preferred solvents are xylene, toluene, halogenated hydrocarbons, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diethylene glycol monobutyl ether.
• MEK methyl ethyl ketone
• MIBK methyl isobutyl ketone
• diethylene glycol monobutyl ether diethylene glycol monobutyl ether.
• the temperature during the dissolution process can be increased.
• Suitable mechanical methods include, for example, brushing, grinding, abrasive polishing, or jet blasting, blasting, or supercritical carbon dioxide blasting.
• a suitable abrasive is, for example, pumice.
• the water jet preferably contains small solid particles, for example, pumice (Al 2 ⁇ 3 ) having an average particle size distribution of 40 to 120 .mu.m, preferably from 60 to 80 .mu.m, and quartz powder (SiO 2 ) with a particle size> 3 microns.
• the oxide layer is at least partially removed.
• the removal of the oxide layer can take place, for example, chemically and / or mechanically.
• Suitable substances with which the base layer can be treated to chemically remove an oxide layer from the electroless and / or electrodepositable particles are, for example, acids such as concentrated or dilute sulfuric acid or concentrated or dilute hydrochloric acid, citric acid, phosphoric acid, amidosulfonic acid, formic acid , Acetic acid.
• Suitable mechanical methods for removing the oxide layer from the electroless and / or electrodepositable particles are generally the same as the mechanical methods of exposing the particles.
• the dispersion applied to the substrate is cleaned by a dry process, a wet chemical process and / or a mechanical process.
• a wet-chemical method is particularly suitable rinsing the substrate with acidic or alkaline reagents or with suitable solvents. Also water in conjunction with ultrasound can be used.
• Suitable acidic or alkaline reagents are, for example, hydrochloric acid, sulfuric acid or nitric acid, phosphoric acid or sodium hydroxide solution, potassium hydroxide solution or carbonates, such as potassium carbonate.
• Suitable solvents are the same as they may be included in the dispersion for applying the base layer. Preferred solvents are alcohols, ketones and hydrocarbons, which are to be selected depending on the substrate material. Also, the oxidizing agents that have already been mentioned in the activation, can be used. Alternatively, prior to transfer of the dispersion by the laser, an additional suitable adhesion layer known to those skilled in the art, a so-called primer, can be applied to the substrate using a coating process known to those skilled in the art.
• Mechanical methods of cleaning the substrate prior to applying the structured or full-surface base layer are generally the same as can also be used to expose the electrolessly and / or electrolytically coatable particles and to remove the oxide layer of the particles.
• dry cleaning processes are particularly suitable. These are, for example, the dedusting by means of brushing and / or deionized air, corona discharge or low-pressure plasma and the removal of particles by means of rollers and / or rollers, which are provided with an adhesive layer.
• the surface tension of the substrate is selectably increased, the substrate surface is cleaned of organic residues and thus improves both the wetting with the dispersion and the adhesion of the dispersion
• the substrate may be provided with an additional adhesive or adhesive layer by methods known to those skilled in the art, if required, prior to the transfer of the base layer.
• the substrate at its top and bottom with an electrically conductive structured or full-surface surface.
• the structured or full-surface electrically conductive surfaces on the upper side and the underside of the carrier can be electrically connected to one another.
• a wall of a bore in the carrier is provided with an electrically conductive surface.
• the bore can be made for example by slitting, punching or laser drilling.
• the electrically conductive structured or full surface on the substrate For coating the electrically conductive structured or full surface on the substrate, this is first supplied to the bath with the electrolyte solution. The substrate is then conveyed through the bath, wherein the electrically conductive particles contained in the previously applied structured or full-surface base layer are contacted with at least one cathode in the case of a galvanic coating. Any customary suitable cathode known to those skilled in the art can be used here. As long as the cathode contacts the structured or solid surface, metal ions are deposited from the electrolyte solution to form a metal layer on the surface. For the contacting, it is also possible to provide auxiliary lines which are connected to the base layer. The contacting with the cathode then takes place via the auxiliary line.
• the base layer itself such as. B. in the use of carbonyl iron powder as a currentless and / or galvanically coatable particles, is not sufficiently conductive, the necessary conductivity for the galvanic coating is achieved by this electroless deposited layer.
• a suitable device in which the patterned or full-surface electrically conductive base layer is electroplated on the substrate generally comprises at least a bath, an anode and a cathode, wherein the bath contains an electrolyte solution containing at least one metal salt. From the electrolytic solution, metal ions are deposited on electrically conductive surfaces of the substrate to form a metal layer.
• the at least one cathode is brought into contact with the base layer of the substrate to be coated or with an auxiliary line, which is in contact with the base layer of the substrate to be coated, while the substrate is conveyed through the bath.
• the Kunststoffels When contacting leads are used for electroplating, they are generally produced in the same way as the base coat.
• the Kunststoffleitersslinien are also preferably at least partially dried and / or cured. After curing, it is also possible for the contacting aids to expose the electroless and / or galva- nisch coatable particles take place.
• the Kunststofftechniksslinien serve, for example, that even short, isolated from each other interconnects can be easily contacted.
• the contacting auxiliary lines are removed again after electroless and / or galvanic metallization. The removal can be done for example by laser ablation, ie by removal with a laser.
• the device for galvanic coating can, for example, be equipped with a device with which the substrate can be rotated.
• the axis of rotation of the device, with which the substrate can be rotated is arranged perpendicular to the surface of the substrate to be coated.
• the layer thickness of the metal layer deposited on the electrolessly and / or electrolytically coatable base layer by the method according to the invention is dependent on the contact time, which results from the passage speed of the substrate through the device and the number of cathodes positioned behind one another, and the current intensity with which the device is operated.
• a higher contact time can be achieved, for example, by connecting several devices according to the invention in series in at least one bath.
• two contacting rollers can be arranged so that the substrate to be coated can be passed between them while being contacted from above and below, whereby metal can be deposited on both sides ,
• endless films which are initially unwound from a roll, passed through the device for electroplating and then wound up again - this can, for example, even zigzag or in the form of a meander around several devices for galvanic coating, which may then be arranged, for example, one above the other or next to one another, through the bath.
• the galvanic coating device may be equipped with any additional device known to those skilled in the art as needed.
• additional devices are, for example, pumps, filters, feeders for chemicals, winding and unwinding devices, etc.
• All methods of care of the electrolyte solution known to those skilled in the art can be used. Such care methods are, for example, systems in which the electrolyte solution regenerates itself.
• the device according to the invention can also be operated, for example, in the pulse method known from Werner Jillek, Gustl Keller, Handbuch der Porterplattentechnik, Eugen G. Leutz Verlag, Volume 4, pages 192, 260, 349, 351, 352, 359.
• the substrate can be processed further in accordance with all steps known to the person skilled in the art. For example, existing electrolyte residues can be removed from the substrate by rinsing and / or the substrate can be dried.
• the process according to the invention for the production of electrically conductive structured or full surface surfaces on a substrate can be operated in a continuous, partially continuous or discontinuous manner. It is also possible that only individual steps of the process are carried out continuously while other steps are carried out discontinuously.
• a structured or full-surface insulation layer can be applied by a printing method as described above.
• a structured or full-surface insulation layer can be applied by a printing method as described above.
• the inventive method is suitable for example for the production of printed conductors on printed circuit boards.
• printed circuit boards are, for example, those with multi-layer internal and external layers, micro-via-chip-on-board, flexible and rigid printed circuit boards. These are incorporated, for example, in products such as computers, telephones, televisions, automotive electrical components, keyboards, radios, video, CD, CD-ROM and DVD players, game consoles, measuring and control devices, sensors, electrical kitchen appliances, electric toys etc. It is also possible with the method according to the invention to produce electrically conductive structures on flexible circuit carriers.
• Such flexible circuit carriers are, for example, plastic films made of the above materials mentioned for the substrate, on which electrically conductive structures are mounted.
• the method according to the invention is suitable for the production of RFI D antennas, transponder antennas or other antenna structures, chip card modules, flat cables, seat heaters, foil conductors, conductor tracks in solar cells or in LCD or.
• the production of contact points or contact pads or wiring on an integrated electronic component is possible.
• antennas with contacts for organic electronic components as well as coatings on surfaces, consisting of electrically non-conductive material for electromagnetic shielding, possible.
• a use is further possible in the field of flowfields of bipolar plates for use in fuel cells.
• the fields of application of the method according to the invention enable a cost-effective production of metallized, even non-conductive substrates, in particular for use as switches and sensors, gas barriers or decorative parts, in particular decorative parts for motor vehicles, plumbing, toys, household and office use and packaging as well as slides. Also in the field of security printing for bills, credit cards, identity papers, etc., the invention can be applied. Textiles can be electrically and magnetically treated with the aid of the method according to the invention. functionalized (antennas, transmitters, RFID and transponder antennas, sensors, heating elements, antistatic (also for plastics), shielding, etc.).
• the method according to the invention can also be used for the metallization of holes, vias, blind holes, etc., for example in printed circuit boards, RFID antennas or transponder antennas, flat cables, foil conductors with the aim of a through-connection of the top and bottom. This also applies if other substrates are used.
• the metallized articles produced according to the invention insofar as they comprise magnetizable metals - are used in areas of magnetizable functional parts, such as magnetic boards. In addition, they find application in areas where a good thermal conductivity is advantageous, for example in films for seat heaters, as well as insulation materials.
• Preferred uses of the metallized surfaces according to the invention are those in which the products thus produced are printed circuit boards, RFI D antennas, transponder antennas, seat heating, flat cables, contactless chip cards, 3D-molded interconnect devices, thin metal foils or one or two-sided laminated polymer supports, film conductors, Conductor tracks in solar cells or in LCD or plasma screens, integrated circuits, resistive, capacitive or inductive elements, diodes, transistors, sensors, actuators, optical components, receiver-transmitting devices or as a decorative application such as for packaging materials used.

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• Engineering & Computer Science (AREA)
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• Microelectronics & Electronic Packaging (AREA)
• Manufacturing Of Printed Wiring (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Laminated Bodies (AREA)
• Manufacturing Of Electric Cables (AREA)

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• 2007
  • 2007-12-21 BR BRPI0720834-0A patent/BRPI0720834A2/pt not_active Application Discontinuation
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